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CN116581385A - Compound additive for lithium battery electrolyte - Google Patents

Compound additive for lithium battery electrolyte Download PDF

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Publication number
CN116581385A
CN116581385A CN202310680300.8A CN202310680300A CN116581385A CN 116581385 A CN116581385 A CN 116581385A CN 202310680300 A CN202310680300 A CN 202310680300A CN 116581385 A CN116581385 A CN 116581385A
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compound
lithium
additive
carbonate
electrolyte
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请求不公布姓名
张振宇
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Tianmu Lake Institute of Advanced Energy Storage Technologies Co Ltd
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Tianmu Lake Institute of Advanced Energy Storage Technologies Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/056Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566Liquid materials
    • H01M10/0567Liquid materials characterised by the additives
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The application discloses a compound additive for lithium battery electrolyte, which comprises a high-voltage additive and an auxiliary additive capable of forming a film together with the high-voltage additive, wherein the high-voltage additive is a polyphosphate compound containing polysubstituted sulfonyl and polysubstituted alkyl structures; the structural general formula of the high-voltage additive is as follows:wherein R is alkyl of 1-8 carbon atoms, X 1 Is one of hydrogen, halogen, C1-8 alkyl or C1-8 halogenated derivative of alkyl, X 2 Is one of hydrogen, halogen, hydrocarbon group with 1-8 carbon atoms or halogenated derivative of hydrocarbon group with 1-8 carbon atoms, and n is polymerization degree.

Description

Compound additive for lithium battery electrolyte
The application relates to a divisional application with the application number of 2021116740415 and the application name of 'high-voltage additive and electrolyte for lithium batteries'.
Technical Field
The application relates to the technical field of materials, in particular to a compound additive for lithium battery electrolyte.
Background
Since a new energy source is provided, the lithium ion battery has a series of advantages of no memory effect, rapid charge and discharge, high energy density, long cycle life, no environmental pollution, etc., and has been widely used in various fields. Nowadays, with the continuous increase of the capacity requirements of pure electric vehicles, hybrid electric vehicles, portable energy storage devices and the like on lithium ion batteries, research and development of lithium ion batteries with higher energy density and power density are expected to realize long-term endurance and energy storage.
The development of the lithium battery with high energy density can lead the anode material and the cathode material to exert higher specific capacity by means of improving the working voltage of the battery, thereby improving the mass energy density and the volume energy density of the lithium ion battery, reducing the cost of the lithium battery and becoming a hot spot for people to study in recent years. However, in the process of researching a high-voltage lithium battery, it is found that along with the increase of the working voltage of the lithium ion battery, the traditional lithium battery electrolyte not only can be subjected to self oxidative decomposition, but also can be subjected to irreversible chemical reaction with a positive electrode material, and active lithium is continuously consumed, so that the battery impedance is increased, the capacity retention rate is low, the performance is deteriorated, and the service life of the battery is seriously shortened, so that the development of a matched electrolyte technology for the high-voltage lithium battery is critical.
Disclosure of Invention
The embodiment of the application provides a compound additive for lithium battery electrolyte, which can form a uniform, compact and stable-performance positive electrode-electrolyte interface phase (CE I) film on the surface of a lithium battery positive electrode material, so that the cycle performance and the storage performance of a lithium battery are improved.
In a first aspect, the present embodiment provides a high voltage additive for lithium battery electrolyte, and an auxiliary additive capable of forming a film together with the high voltage additive, wherein the high voltage additive is a polyphosphate compound containing polysubstituted sulfonyl and polysubstituted alkyl structures; the structural general formula of the high-voltage additive is as follows:
wherein R is alkyl of 1-8 carbon atoms, X 1 Is one of hydrogen, halogen, C1-8 alkyl or C1-8 halogenated derivative of alkyl, X 2 Is one of hydrogen, halogen, hydrocarbon group with 1-8 carbon atoms or halogenated derivative of hydrocarbon group with 1-8 carbon atoms, and n is polymerization degree.
Preferably, the halogen includes: one or more of fluorine, chlorine or bromine; the hydrocarbon group includes: one or more of alkyl, alkenyl, cycloalkenyl or aryl; the halogenated derivative of the hydrocarbon group is specifically a halogen partially or fully substituted hydrocarbon group.
In a second aspect, the present embodiment provides an electrolyte for a high voltage lithium battery, the electrolyte comprising: a lithium salt electrolyte, an organic solvent, a high voltage additive as described in the first aspect above, and an auxiliary additive.
Preferably, the lithium salt electrolyte includes: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl imide) or lithium bis (fluorosulfonyl imide).
Preferably, the organic solvent includes: any one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, and halogenated derivatives thereof.
Preferably, the auxiliary additive comprises: cyclic carbonate compounds, linear ester compounds containing unsaturated bonds, cyclic sulfate compounds, cyclic sulfonate compounds, silazane compounds, sulfonic acid amine salt compounds, phenylborane compounds, silicon-containing phosphate compounds, cyclic carboxylic acid borate compounds, nitrile compounds or sulfone compounds.
Preferably, the cyclic carbonate compound, the linear ester compound having an unsaturated bond, the cyclic sulfate compound, the cyclic sulfonate compound, the silazane compound, the amine sulfonate compound, the phenylborane compound, the siliceous phosphate compound, the cyclic carboxylate borate compound, the nitrile compound or the sulfone compound may be substituted with a fluorine-containing substituent.
Preferably, the cyclic carbonate compound comprises one or more of vinylene carbonate and vinyl ethylene carbonate;
the linear ester compound containing unsaturated bond comprises ethylene vinyl acetate;
the cyclic sulfate compound comprises one or more of ethylene sulfite, propylene sulfite and ethylene sulfate;
the cyclic sulfonate compound comprises one or more of 1, 3-propane sultone, propenyl-1, 3-propane sultone, 1, 4-butane sultone and methyl disulfonate;
the silazane compound comprises hexamethyldisilazane;
the silicon-containing phosphate compound comprises tris (trimethylsilyl) phosphate and tris (trimethylsilyl) phosphite;
the sulfonic acid amine salt compound comprises magnesium triflate imine;
the phenylborane-based compound comprises tris (pentafluorophenyl) boron;
the cyclic carboxylate borate compound includes lithium difluorooxalato borate.
Preferably, in the electrolyte, the mass of the lithium salt electrolyte accounts for 0.5-20 wt% of the total mass of the electrolyte;
the mass of the organic solvent accounts for 70-90% of the total mass of the electrolyte;
the mass of the high-voltage additive accounts for 0.1-5 wt% of the total mass of the electrolyte;
the mass of the auxiliary additive accounts for 1-5 wt% of the total mass of the electrolyte.
In a third aspect, the present embodiment provides a high-voltage lithium battery, which includes the electrolyte for a high-voltage lithium battery according to the second aspect.
Preferably, the positive electrode material of the high-voltage lithium battery includes: one or more of lithium cobaltate, lithium manganate, lithium nickel manganate, lithium-rich material, nickel cobalt manganese ternary material or nickel cobalt aluminum material.
The high-voltage addition for the lithium battery provided by the embodiment of the application is a polyphosphate compound containing polysubstituted sulfonyl and polysubstituted alkyl structures, and in the structure, due to the influence of polysubstituted groups on sulfonyl functional groups, the polyphosphate compound is easy to oxidize and decompose under high voltage to form some sulfur-containing inorganic compounds. Meanwhile, the polysubstituted alkyl is oxidized, and forms a uniform and compact CEI film on the surface of the positive electrode material together with the sulfur-containing compound, wherein the CEI film contains phosphorus and sulfur or halogen, has stable components and better mechanical properties, and can fully cover the surface of the positive electrode material, thereby inhibiting the breakage of positive electrode material particles under high voltage.
Under high voltage, a large amount of phosphate functional groups can complex transition metal ions dissolved out from the surface of the positive electrode material, so that the transition metal ions with high oxidability are prevented from entering the electrolyte and reaching the negative electrode material, and the continuous oxidation of the electrolyte and the damage of the negative electrode material are reduced.
The high-voltage additive modifies the electrode/electrolyte interface through the action of the multifunctional groups, so that the surface of the positive electrode material is prevented from being in direct contact with the electrolyte, and further the oxidative decomposition of the electrolyte is reduced. The CEI film has stable components, can not be dissolved and regrown in the battery charge-discharge cycle process, improves the uniformity of the CEI film, reduces the thickness of the CEI film, reduces the impedance of the battery and reduces polarization. The high-voltage additive can also form a film together with an auxiliary additive on the negative electrode to form a composite negative electrode Solid Electrolyte Interface (SEI) film, so that the stability of the negative electrode SE I film is improved, and the electrochemical performance of the lithium battery under the high-voltage condition is improved.
Detailed Description
The present application is further illustrated by the following specific examples, which are to be understood as being for the purpose of more detailed description only and are not to be construed as limiting the application in any way, i.e. not intended to limit the scope of the application.
The embodiment of the application provides a high-voltage additive for lithium battery electrolyte, which is a polyphosphate compound containing polysubstituted sulfonyl and polysubstituted alkyl structures; the structural general formula of the high-voltage additive is as follows:
wherein R is alkyl of 1-8 carbon atoms, X 1 Is one of hydrogen, halogen, C1-8 alkyl or C1-8 halogenated derivative of alkyl, X 2 Is one of hydrogen, halogen, hydrocarbon group with 1-8 carbon atoms or halogenated derivative of hydrocarbon group with 1-8 carbon atoms, and n is polymerization degree.
Halogen includes: one or more of fluorine, chlorine or bromine; the hydrocarbon group includes: one or more of alkyl, alkenyl, cycloalkenyl or aryl; the halogenated derivatives of hydrocarbyl groups are specifically halogen partially or fully substituted for hydrogen in the hydrocarbyl group.
The embodiment of the application provides an electrolyte for a high-voltage lithium battery, which comprises the following components: lithium salt electrolyte, organic solvent, high voltage additive and auxiliary additive.
The lithium salt electrolyte includes: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl imide) or lithium bis (fluorosulfonyl imide); wherein the mass of the lithium salt electrolyte accounts for 0.5-20wt% of the total mass of the electrolyte.
The organic solvents include: any one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate and halogenated derivatives thereof; wherein the mass of the organic solvent accounts for 70-90 wt% of the total mass of the electrolyte.
The high-voltage additive is the polyphosphonate compound containing the polysubstituted sulfonyl and polysubstituted alkyl structures, and the mass of the high-voltage additive accounts for 0.1-5 wt% of the total mass of the electrolyte. The high-voltage additive can form a film preferentially in the charging and discharging process of the battery, form a uniform and compact CE I film on the surface of the positive electrode, modify the interface of the positive electrode material and the electrolyte, reduce the oxidative decomposition of the electrolyte, improve the stability of the electrolyte under high voltage and improve the high-voltage electrochemical performance of the lithium battery. After the high-voltage additive is added, the high-voltage cycle capacity retention rate and the high-voltage cycle life of the lithium battery are improved to a certain extent within a proper adding range.
The auxiliary additive comprises: one or more of vinylene carbonate, ethylene carbonate, ethylene vinyl acetate, ethylene sulfite, propylene sulfite, ethylene sulfate, 1, 3-propane sultone, propenyl-1, 3-propane sultone, 1, 4-butane sultone, methylene methylsulfonate, hexamethyldisilazane, magnesium trifluoromethane sulfonate, tris (phenyl pentafluoride) boron, tris (trimethylsilane) phosphate, tris (trimethylsilane) phosphite, lithium difluorooxalato borate, nitrile compound or sulfone compound; wherein the mass of the auxiliary additive accounts for 1-5 wt% of the total mass of the electrolyte. The auxiliary additive and the high-voltage additive can form a composite SE I film on the negative electrode, so that the stability of the negative electrode SE I film is improved, and the electrochemical performance of the lithium battery under the high-voltage condition is improved.
The embodiment of the application provides a high-voltage lithium battery, which comprises the electrolyte for the high-voltage lithium battery. Wherein, the positive electrode material of the high voltage lithium battery comprises: one or more of lithium cobaltate, lithium manganate, lithium nickel manganate, lithium-rich material, nickel cobalt manganese ternary material or nickel cobalt aluminum material.
For better understanding of the technical scheme provided by the application, the preparation of the electrolyte with the high-voltage additive and the method and the battery characteristics applied to the lithium battery are respectively described in the following specific examples.
Example 1
The embodiment provides a high-voltage additive A, which has the following structural formula:
in argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the mass ratio of less than or equal to 2.0ppm, mixing organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare an electrolyte with the concentration of 1mol/L lithium hexafluorophosphate, and then adding auxiliary additives of ethylene carbonate (VC), succinonitrile (SN) and lithium difluoroborate (LiDFOB) according to mass fractions of 1%, 1% and 0.5%, respectively, and then adding 1% of high-voltage additive A to prepare the electrolyte I.
The electrolyte prepared in this example was used to assemble lithium batteries and tested as follows:
(1) Selecting lithium cobalt oxide suitable for high voltage as a positive electrode material, and adding LiCoO as the positive electrode material 2 Uniformly mixing Carbon Nanotubes (CNTs) and polyvinylidene fluoride (PVDF) according to the ratio of 98:1:1, coating on an aluminum foil current collector, drying the aluminum foil current collector by an oven, rolling the aluminum foil current collector on a roll squeezer, and compacting the aluminum foil current collector to a compaction density of 4.0g/cm 3 The required positive plate is obtained.
(2) Artificial graphite is selected as a negative electrode material, and an artificial negative electrode, carboxymethyl cellulose (CMC), a conductive agent Super P and a binder Styrene Butadiene Rubber (SBR) are mixed according to the following ratio of 95:1.2:1.8:2, and the mixture is uniformly mixed to prepare the negative plate, wherein the compacted density of the plate is 1.65g/cm 3 .
(3) PE with the thickness of 9 mu m is selected as a base film, a ceramic material with the thickness of 3 mu m is coated, a (9+3) coating isolation film is obtained, and a pole piece is manufactured into a small soft package battery with the thickness of 2Ah through a lamination method, wherein electrolyte prepared in the embodiment is adopted.
The performance of the electrolyte of this example was measured by testing a small pouch cell, i.e., evaluating the effect of the high voltage additive. The test conditions were: the charge-discharge voltage window is 3.0-4.5V, the cycle test is respectively carried out at room temperature of 25 ℃ and high temperature of 45 ℃, and the cycle charge-discharge current is 0.5 ℃.
The battery numbers 1# prepared in this example and the test results are shown in Table 1.
Example 2:
the present embodiment provides a high voltage additive B:
in argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the mass ratio of less than or equal to 2.0ppm, mixing organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare an electrolyte with the concentration of 1mol/L lithium hexafluorophosphate, and then adding auxiliary additives of VC, SN and LiDFOB according to mass fractions of 1%, 1% and 0.5%, respectively, and then adding 1% of a high-voltage additive B to prepare the electrolyte II.
The electrolyte prepared in this example was used to assemble a lithium battery and tested, lithium manganate was used as the positive electrode material, the specific steps and testing procedure of battery assembly were the same as those of example 1, the battery number 2# prepared in this example was shown in table 1.
Example 3:
the present embodiment provides a high voltage additive C:
in argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the concentration of less than or equal to 2.0ppm, the organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) are prepared according to the following stepsMixing EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare electrolyte with the concentration of lithium hexafluorophosphate of 1mol/L, adding auxiliary additives VC, SN and LiDFOB according to mass fractions of 1%, 1% and 0.5%, and then adding 1% of high-voltage additive C to prepare electrolyte III.
The electrolyte prepared in this example was used to assemble a lithium battery and tested, and lithium cobaltate was used as the positive electrode material, and the specific steps and test procedures for battery assembly were the same as those in example 1, and the battery number 3# prepared in this example was shown in table 1.
Example 4:
the present embodiment provides a high voltage additive D:
in argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the concentration of less than or equal to 2.0ppm, mixing organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare an electrolyte with the concentration of 1mol/L lithium hexafluorophosphate, and then adding auxiliary additives of VC, SN and LiDFOB according to mass fractions of 1%, 1% and 0.5%, respectively, and then adding 1% of high-voltage additive D to prepare the electrolyte IV.
The electrolyte prepared in this example was used to assemble a lithium battery and tested, lithium nickel manganese oxide was used as the positive electrode material, the specific steps and testing procedure of battery assembly were the same as those of example 1, the battery number 4# prepared in this example, and the test results are shown in table 1.
Example 5:
this example uses the same high voltage additive B as example 2:
in argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the concentration of less than or equal to 2.0ppm, mixing organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare an electrolyte with the concentration of 1mol/L lithium hexafluorophosphate, and then adding auxiliary additives of VC, SN and LiDFOB according to mass fractions of 1%, 1% and 0.5%, respectively, and then adding a high-voltage additive of 0.5% to prepare an electrolyte V.
The electrolyte prepared in this example was used to assemble a lithium battery and tested, and a nickel-cobalt-manganese ternary material was used as a positive electrode material, and the specific steps and test procedures for battery assembly were the same as those in example 1, and the battery number 5# prepared in this example was shown in table 1.
Example 6:
this example uses the same high voltage additive B as example 2:
in argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the mass ratio of less than or equal to 2.0ppm, mixing organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare an electrolyte with the concentration of 1mol/L lithium hexafluorophosphate, and then adding auxiliary additives of VC, SN and LiDFOB according to mass fractions of 1%, 1% and 0.5%, and then adding a high-voltage additive of 1.5%, thereby preparing an electrolyte VI.
The electrolyte prepared in this example was used to assemble a lithium battery and tested, and a lithium-rich material was used as a positive electrode material, and the specific steps and test procedures for assembling the battery were the same as those in example 1, and the battery number 6# prepared in this example was shown in table 1.
Example 7:
this example uses the same high voltage additive B as example 2:
in argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the concentration of less than or equal to 2.0ppm, mixing organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare an electrolyte with the concentration of 1mol/L lithium hexafluorophosphate, and then adding auxiliary additives of VC, SN and LiDFOB according to mass fractions of 1%, 1% and 0.5%, respectively, and then adding a high-voltage additive of 2% to prepare an electrolyte VII.
The electrolyte prepared in this example was used to assemble a lithium battery and tested, and a nickel cobalt aluminum material was used as the positive electrode material, and the specific steps and test procedures for battery assembly were the same as those in example 1, and the battery number 7# prepared in this example was shown in table 1.
To better illustrate the effect of the examples of the present application, comparative example 1 is compared with the above examples.
Comparative example 1:
the high voltage additives were not used in this comparative example.
In argon atmosphere, the environmental index is H 2 O≤0.5ppm,O 2 In a glove box with the concentration of less than or equal to 2.0ppm, mixing organic solvents of Ethylene Carbonate (EC), propylene Carbonate (PC), fluoroethylene carbonate (FEC) and methyl ethyl carbonate (EMC) according to the mass ratio of EC/PC/FEC/EMC=15/10/5/70, adding lithium hexafluorophosphate for dissolution to prepare an electrolyte with the concentration of 1mol/L lithium hexafluorophosphate, and then adding auxiliary additives of VC, SN and LiDFOB according to mass fractions of 1%, 1% and 0.5%, respectively, so as to prepare the comparative electrolyte 1.
The electrolyte prepared in this comparative example was used to assemble a lithium battery and tested, using lithium cobalt oxide as the positive electrode material, and the battery was assembled in the same manner as in example 1, with the battery number 8# prepared in this comparative example, and the test results are shown in table 1.
Table 1 shows the results of the electrical performance tests of the assembled batteries of examples 1 to 7 and comparative example 1.
TABLE 1
As can be seen from the data in table 1, the battery first efficiency and the cycle capacity retention rate of the embodiments 1 to 7 of the present application are both superior to those of the comparative example 1, which shows that after the high voltage additive of the present application is used, the normal temperature first efficiency, the normal temperature cycle capacity retention rate and the high temperature cycle capacity retention rate of the high voltage lithium battery are all improved to some extent within a proper addition range. The high-voltage additive disclosed by the application has excellent performance, and the high-voltage electrolyte prepared by using the high-voltage additive is good in liquid performance.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.

Claims (10)

1. The compound additive for the lithium battery electrolyte is characterized by comprising a high-voltage additive and an auxiliary additive capable of forming a film together with the high-voltage additive, wherein the high-voltage additive is a polyphosphate compound containing polysubstituted sulfonyl and polysubstituted alkyl structures; the structural general formula of the high-voltage additive is as follows:
wherein R is alkyl of 1-8 carbon atoms, X 1 Is one of hydrogen, halogen, hydrocarbon group with 1-8 carbon atoms or halogenated derivative of hydrocarbon group with 1-8 carbon atoms,X 2 is one of hydrogen, halogen, hydrocarbon group with 1-8 carbon atoms or halogenated derivative of hydrocarbon group with 1-8 carbon atoms, and n is polymerization degree.
2. The compound additive for lithium battery electrolyte according to claim 1, wherein the ratio of the high-voltage additive to the auxiliary additive is (1-2 parts) 2.5 parts by mass.
3. The additive package for lithium battery electrolyte according to claim 1, wherein the halogen comprises: one or more of fluorine, chlorine or bromine; the hydrocarbon group includes: one or more of alkyl, alkenyl, cycloalkenyl or aryl; the halogenated derivative of the hydrocarbon group is specifically a halogen partially or fully substituted hydrocarbon group.
4. The additive package for lithium battery electrolyte according to claim 1, wherein the auxiliary additive comprises: cyclic carbonate compounds, linear ester compounds containing unsaturated bonds, cyclic sulfate compounds, cyclic sulfonate compounds, silazane compounds, sulfonic acid amine salt compounds, phenylborane compounds, silicon-containing phosphate compounds, cyclic carboxylic acid borate compounds, nitrile compounds or sulfone compounds.
5. The compound additive for lithium battery electrolyte according to claim 4, wherein the cyclic carbonate compound, the linear ester compound containing unsaturated bonds, the cyclic sulfate compound, the cyclic sulfonate compound, the silazane compound, the amine sulfonate compound, the phenylborane compound, the siliceous phosphate compound, the cyclic carboxylate borate compound, the nitrile compound or the sulfone compound can be substituted by fluorine-containing substituent groups.
6. The compound additive for lithium battery electrolyte according to claim 4, wherein the cyclic carbonate compound comprises one or more of vinylene carbonate and vinyl ethylene carbonate;
the linear ester compound containing unsaturated bond comprises ethylene vinyl acetate;
the cyclic sulfate compound comprises one or more of ethylene sulfite, propylene sulfite and ethylene sulfate;
the cyclic sulfonate compound comprises one or more of 1, 3-propane sultone, propenyl-1, 3-propane sultone, 1, 4-butane sultone and methyl disulfonate;
the silazane compound comprises hexamethyldisilazane;
the silicon-containing phosphate compound comprises one or more of tris (trimethylsilyl) phosphate and tris (trimethylsilyl) phosphite;
the sulfonic acid amine salt compound comprises magnesium triflate imine;
the phenylborane-based compound comprises tris (pentafluorophenyl) boron;
the cyclic carboxylate borate compound includes lithium difluorooxalato borate.
7. Use of the built additive of any one of claims 1-6 in an electrolyte.
8. The use according to claim 7, wherein the electrolyte further comprises a lithium salt electrolyte, an organic solvent.
9. The use according to claim 8, wherein the lithium salt electrolyte comprises: one or more of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium tetrafluoroborate, lithium difluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bis (trifluoromethylsulfonyl imide) or lithium bis (fluorosulfonyl imide).
10. The electrolyte of claim 8, wherein the organic solvent comprises: any one or more of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propyl carbonate, 1, 4-butyrolactone, methyl formate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, ethyl butyrate, and halogenated derivatives thereof.
CN202310680300.8A 2021-12-31 2021-12-31 Compound additive for lithium battery electrolyte Pending CN116581385A (en)

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